Non-ionic surface active agents as cosmetic emulsifiers

ABSTRACT

An emulsifying and peptizing agent having the formula ROC2H3O(R&#39;&#39;))m (C2H3O(X))nH wherein R is a lipophilic hydrocarbon residue of a member selected from the group consisting of alcohols, sterols and their mixtures derived from a member selected from the group consisting of (a) hydrogenated lanolin, and (b) cyclic fatty acids, R&#39;&#39; is selected from the group consisting of methyl and ethyl, X is selected from the group consisting of -CH2O-C2H3O(CH2OH))p CH2-CHOH-CH2OH, m has a statistical average value between 1-10 inclusive, N HAS A STATISTICAL AVERAGE VALUE BETWEEN 1-5 INCLUSIVE, P IS AN INTEGER BETWEEN 0-10 INCLUSIVE AND THE PRODUCT N(P+2) LIES BETWEEN 2-12 INCLUSIVE.

United States Patent [1 1 Kalopissis et al.

[ Oct. 21, 1975 [54] NON-IONIC SURFACE ACTIVE AGENTS AS COSMETICEMULSIFIERS [75] Inventors: Gregoire Kalopissis, Paris; Guy

Vanlerberghc, Montjay-la-Tour, both of France [73] Assignee: SocieteAnonyme Dite: LOreal, Paris, France [22] Filed: June 17, 1974 I 21 Appl.No.: 480,671

Related U.S. Application Data [60] Division of Ser. No. 119,363, Feb.26, 1971, Pat. No. 3,824,294, which is a continuation-in-part of Ser.No. 780,299, Nov. 29, 1968, abandoned, which is a continuation-in-partof Ser. No. 677,047, Oct. 23, 1967, Pat. No. 3,595,924.

[30] Foreign Application Priority Data Oct. 21, 1966 France 66.52227Oct. 24, 1966 France..... 66.52228 Oct. 6, 1967 France 67.54662 Dec. 1,1967 France 67.130712 [52] U.S. Cl. 424/63; 8/101; 252/DIG. 1;

[51] Int. Cl. ..A61K 7/021; A61K 7/035; A61K 9/10 [58] Field of Search424/63, 69, 64, 170, 365; 252/316; 260/611 B [56] References CitedUNITED STATES PATENTS 3,578,719 5/1971 Kalopissis et al. 424/63 X3,594,409 7/1971 Lachampt et al 424/365 X Primary Examiner-Albert T.Meyers Assistant ExaminerVera C. Clarke Attorney, Agent, or FirmCushman,Darby & Cushman [57] ABSTRACT An emulsifying and peptizing agent havingthe formula R0 2 3. T C2H3O(X) '1n H CHQOH CHgO+C3H30(CHgOH) 11T CHgCHOH CH2OH.

m has a statistical average value between 1-10 inclusive,

n has a statistical average value between 1-5 inclusive,

p is an integer between 0-10 inclusive and the product n(p+2) liesbetween 212 inclusive.

7 Claims, N0 Drawings NON-IONIC SURFACE ACTIVE AGENTS AS COSMETICEMULSIFIERS This is a division, of application Ser. No. 119,363 filedFeb. 26, 1971 now U.S. Pat. No. 3,824,294 which is acontinuation-in-part of Ser. No. 780,299 filed Nov. 29, 1968, nowabandoned, which is a continuation-inpart of Ser. No. 677,047, filedOct. 23, 1967, now U.S. Pat. No. 3,595,924.

The present invention relates to chemical compounds usefully employed ascosmetic emulsifiers or peptizers. These compounds are non-toxic and donot become rancid. The present invention is also related to a method forpreparing these new chemical compounds.

In accordance with the present invention, there is provided a chemicalcompound having the formula R-[-C H=O(R')] [-C H O(XH-;, H (I) wherein Ris a lipophilic hydrocarbon residue of a member selected from the groupconsisting of alcohols sterols or their mixtures derived from a memberselected from the group consisting of (a) hydrogenated lanolin, and (b)cyclic fatty acids,

R is selected from the group consisting of methyl and ethyl,

X is selected from the group consisting of CH OH.

m has a statistical average value between 1-10 inclusive, preferablybetween 2-6 inclusive,

n has a statistical average value between 1-5 inclusive,

p is an integer between 0l0 inclusive and the product n(p 2) liesbetween 2-12, inclusive.

The method of the present invention for producing these novel compoundscomprises the steps of( l polycondensing on a compound having theformula ROH wherein R has the meaning given above an epoxide having theformula wherein R has the meaning given above and thereafter a halogencontaining member having the formula wherein Y is selected from thegroup consisting of CH Z,

wherein Z is selected from the group consisting of chlorine and bromine,at a temperature between 25 Cl5() C in the presence of an acid catalystselected from the group consisting of boron fluoride, antimonypentachloride and stannic chloride, (2) hydroxylating the resultingcondensate from (1) by esterifying with alkaline acetat at a temperaturebetween C2()0C in the presence of a solvent selected from the groupconsisting of propylene glycol, dipropylene glycol, diethylene glycol.the ethers of diethylene glycol. ethylene glycol, hexylene glycol andZ-butoxy ethanol. said alkaline acetate being present in amounts rangingbetween stoichiometric and 1571 in excess of stoichiometry based on saidhalogen containing member and said solvent being present in amounts ofat least 507r of said halogen-containing member and (3) deacylating byalcoholysis the ester formed in (2) above.

One object of the present invention is to enlarge the class of non-ionicsurface active agents described in our aforementioned earlierapplications by adding thereto those which can be prepared from naturalor synthetic aliphatic or alicyclic alcohols and/or sterols having ahigh molecular weight. By natural alcohols and sterols are meant thosederived, for example, from hydrogenated lanolin, and from reduced cyclicfatty acids.

It is known, for instance, that the lanolin alcohols comprise up to 30carbon atoms and that they consist of a mixture of the aliphatic serieshaving straight or branched chains (iso and anteiso derivatives) andalcohols of the alicyclic series (sterols and triterpenic alcohols). Thealcohols are found in lanolin, essentially in the form of esters offatty acids. Hydrogenation yields a mixture containing both alcoholsfrom the unsaponifiable constituents and those from the fatty acids oflanolin.

The preparation oflanolin alcohols by hydrogenation was described byStockdorn, E. Konig and Birk in the Tenside review, 3, No. 2 (1966)p.45.

Elrolan" sold by VEB Deutsches Hydrierwerk and Hydrolan R" sold by OccoInternational, Division of Millmaster Onyx Corporation, Jersey City, NewJersey U.S.A. are examples of alcohols of lanolin prepared byhydrogenation.

Representative cyclic fatty alcohols derived from cyclic fatty acidsinclude those of the following form ulae wherein x y 10 and Thenon-ionic surface active agents envisaged by the present application canbe employed in emulsions containing as an emulsifier a compound havingformula (I) and especially in cosmetic products, for example inhydrating creams or nourishing creams, or in pharmaceutical excipients.They can also be used as carriers for hair dyes. For example, hair dyessold in gel form, containing a compound having formula (I).Additionally, the compounds of this invention can be used to producedispersions of solid pulverulent products in liquid media and especiallyin oils. The novel compounds of this invention are employed as peptizingagents to produce such dispersions.

The compounds having the above formula (I) are, in general, emulsifierswhich make it possible to form water-in-oil emulsions, especially whenthe product n (p-l-Z) is less than about 4. In such emulsion. water ispresent in amounts of about to 70 weight percent, oil in amounts ofabout to 70 weight percent and the emulsifiers in amounts of about 5 to25 weight percent.

When the product n (p+2) is greater than about 4, the compounds offormula (I) are generally employed as emulsifiers to produce Oilin-wateremulsions. These emulsions comprise about to weight percent water, 30 to60 weight percent oil and 10 to 25 7 weight percent of said emulsifier.

It should be noted that, in a given compound, the R radicals which aresubstituents on the ethoxamer can be identical or different. In thelatter case. they may be distributed in various proportions, either inregular sequences or in an irregular manner, depending on whether thepure epoxides are poly added in several distinct steps or mixtures ofpropylene oxide and butyl ene oxide are used.

In a preferred embodiment of the present invention, polycondensation iscarried out in an autoclave or in a container connected to the ambientatmosphere through a reflux condenser. When the polycondensationcatalyst is boron fluoride. this is used in the form of a complex withacetic acid or ether. The quantity of boron fluoride in terms of BF per100g of reactants, is between 0. 1'7: and 1%, and preferably about04-05%. The temperature should preferably be kept below 100C, forexample and C.

The hydroxylation which constitutes the second step of the process isbased on the reaction of the halogen derivative obtained in the firststep with an alkaline salt of carboxylic acid, preferably in a solventbath which insures both the miscibility of the reactants and the easyseparation of the mineral halide formed. In this method, the selectedsolvents participate through progressive alcoholysis of the estersformed in an intermediate stage. Among the solvents having the requiredproperties are propylene glycol, dipropylene glycol, diethylene glycol.the ethers of diethylene glycol, ethylene glycol, hexylene glycol, and2-butoxy ethanol, the boiling points of which are high enough to makethe use of an autoclave unnecessary. In general, it has been found thatthe quantity of solvent to be used during hydroxylation should b atleast 50% as much by weight as the polyhalogenated ether which is to behydroxylated, and preferably between and 400 as much. The hydroxylationis carried out at a temperature high enough to complete the reactionwithin a reasonable length of time, and low enough to avoid degradationof the products formed. A temperature between C and 200C, and preferablybetween 180C and C satisfies these conditions. About 90 7: hydroxylationresults.

The alkaline salt of carboxylic acid used in the process mayadvantageously be an alkaline acetate such as potassium acetate, sodiumacetate and the like employed in a stoichiometric proportion, or inslight excess (10 to 15% at most) with respect to the halogenatedcompounds participating in the reaction. It has been found that theresults are equally satisfactory regardless of whether the acetates areadded all at once at the beginning of the hydroxylation step, or insuccessive stages during the course of this reaction. It is possible toregenerate the acetates in situ from the esters formed during thereaction. for example. by adding an aqueous solution ofa correspondingalkaline hydroxide and instantaneously evaporating the water.

In order to avoid coloring the products obtained during hydroxylationreducing agents such as sodium hypophosphite or alkaline borohydridesmay be added.

The crude products obtained by this process may advantageously bepurified by washing them in hot water. The water soluble impurities, andparticularly the electrolytes are thus eliminated and this isparticularly desirable when the water-in-oil type of emulsion isprepared.

When the products of formula (I) are to be used in emulsions of thewater-in-oil type. the preferred products are those having a relativelyshort hydrophile chain in which n has, for example, a value between 2and 3 and X represents hydroxymethyl.

When the products of formula (I) are to be used in emulsions of theoil-in-water type, the preferred products are those having a relativelylong hydrophile chain, in which, for example, n is greater than 3 when Xrepresents hydroxymethyl.

The following oils illustrate the kind of oil that could be used in thewater-in-oil or in the oil-in-water type of emulsion:

l. hydrocarbons such as paraffin oil, liquid petrolatum, squalane orperhydrosqualene;

2. animal and vegetable oils such as horse grease, lard, lard oil,sweet-almond oil, peanut oil, olive oil, calophyllum;

3. esters such as oleyl oleate, isopropyl myristate, isopropyl palmitateand isopropyl stearate.

When emulsifiers which are strongly hydrophilic are desired, the valueof n should be greater than 1 and, better yet. when X represents the CHOH radical, at least equal to 2. Moreover, the parameter m should have avalue high enough so that the oxypropylenated or oxybutylenated alcoholobtained in the first polycondensation step has a melting point below40C. The lower limits of m and n are thus determined by thephysiochemical properties of the emulsifiers produced.

The non-ionic surface-active agents of this invention can be used asemulsifiers in formulating cosmetic compositions or pharmaceuticalexcipients, as carriers for hair dyes, or as peptizers in producingdispersions of pulverulent products. They are non-toxic, even whenapplied to the skin, which is a very important criterion when cosmeticapplications are envisaged.

The present invention is also directed to emulsions which can be used,particularly in cosmetic products or in pharmaceutical excipients,essentially characterized by the fact that they contain, as anemulsifier, at least one compound according to formula (I).

In the cosmetic field the compounds according to formula (I) can serveas bases for hydrating milks, cleansing creams, or nourishing creams.They can also be used as carriers for hair dyes, and in that case mayproduce such dyes in the form of a gel.

Another object of the present invention is therefore to provide a dyecomposition for human hair essentially characterized by the fact that itcomprises as a carrier at least one compound according to formula (I) inamounts of about to 30 weight percent based on dye composition mixedwith conventional cosmetic hair dye.

The new chemical compounds according to formula (I) can also act aspeptizing agents, which are particularly efficacious in dispersing solidpowdered material in liquid media, and especially in oil. Generally thepeptizing agent will be present in amounts of about 5 to weight percentof the solid powdered material.

It is therefore another object of the present invention to providedispersions of solid pulverulentproducts in liquid media andparticularly in oils, characterized by the fact that they contain aspeptizing agents at least one compound according to formula (I).

To illustrate the invention, several examples thereof will now bedescribed.

EXAMPLE 1 Preparation of the product represented by the R0-[-C,H,o CH,-4=C,H,O(CH,0H ,-H in which R represents a hydrocarbon residue derivedfrom a lanolin alcohol obtained by catalytic hydrogenation of lanolinand sold under the trademark ELRO- LAN by VEB DEUTSCHES HYDRIERWERK.

for-

First Step: Polycondensation of propylene oxide and epichlorohydrinSecond Step: Hydroxylation 62 g of the chlorinated polyether thusobtained is added to 15.7 g of potassium acetate dissolved in 80 g ofdipropylene glycol. The reaction mixture is heated to l80185C for 3hours and minutes under a nitrogen atmosphere.

After cooling to 70C, the potassium chloride is separated by filtrationand the precipitate washed with 50 g of hot dipropylene glycol. Thesolvent is evaporated from the filtrate, under a vacuum, while it isbeing agitated, and whileincreasing the temperature progressively to185C. The crude product obtained in this manner has a saponificationindex of 22 mg KOH/g. The product is then subjected toethanolysis bydissolving it in 100 ml of absolute ethyl alcohol and adding sodiummethylate as a catalyst at the rate of 0.275 g per 100 g of the-productto be treated.

The alcoholic solution is left overnight at ambient temperature and thenbleached with animal charcoal. After evaporation of the ethyl acetateand the alcohol, an amberyellow solid is recovered, the averagecomposition of which is given at the beginning of this example. It canbe purified by washing with a hydroalcoholic solution containing 15%ethyl alcohol.

EXAMPLE 2 Fluid skin treating cream The following composition isprepared:

Compound of Example 1 9 g Lanolin alcohol sold under the trademark SuperHartolan" by the Croda Compnay 4 g Vaseline 11.5 g Pcrhydrosqualcne 10 gMicrocrystallinc wax 4.5 g Water, q.s.p. 100 g The scope of theinvention is not limited to the foregoing examples, and the examplescould be modified as to detail without departing from the basicprinciples of the invention. In particular the hydrophilic property ofthe compounds of the invention could be increased by subsequent reactionwith one or more molecules of ethylene oxide. Moreover, the compoundsaccording to the invention may be transformed by known processes, intoionic surface-active agents by introducing ionic groups into thecompound structure as sulfonate ions, carboxylate ions, phosphate ions,etc.

Although the examples set forth above use R groups obtained by reactingcommercially available fatty alcohol mixtures similar results can beobtained by using a single fatty alcohol or sterol.

The cosmetic compositions according to the present invention maycontain, apart from the cosmetics and the compound of formula (1),different adjuvants, for example oil retention ingredients such aslanolin alcohols and microcrystalline waxes.

EXAMPLE 3 This example relates to the peptization of a pulverulentsolid, hydrated iron oxide.

Iron oxides are often used in cosmetic compositions but before use theygenerally have to be washed in order to eliminate impurities. Upondrying they tend to ball together. This re-agglomeration can be avoidedby adding in the last washing a surface active agent having the generalformula (I).

The present example relates to iron oxide sold under the trademarkMicronPink 2511" sold by Thomasset Color.

5% weight of the compound of Example 1 is added in the last washing ofthe iron oxide. After carefully drying, the resulting powder isperfectly wetted by oils and can be introduced in cosmetic compositions.

Other iron oxides as well as other pigments such as titanium oxides,barium sulfate and Guimets blue can be peptized in this manner withequally favorable results.

What is claimed is:

l. A water-in-oil emulsion comprising 20 to water, 25 to 70% oil and asan emulsifier, 5 to 25% of a compound having the formula:

RO[-C,H O(R')-};riz l'l|- wherein R is a lipophilic hydrocarbon residueof a member selected from the group consisting of hydrogenated lanolin,

(CHUr-CHzOl'l,

wherein 3. A skin treating cream composition comprising a water-in-oilor oil-in-water medium and an emulsifying amount of a compound havingthe formula 5 wherein R is a lipophilic hydrocarbon residue of a memberselected from the group consisting of hydrogenated lanolin.

wherein x +y l2.

R is selected from the group consisting of methyl and ethyl. 10 X isselected from the group consisting of (CH2) CH2OH CH OH.

(CH ),,CH

CH OH l5 CH OH I wherein x v 10 and and CH O{-C H -,O(CH OH)hrCHCHOH-CH- m has a statistical average value between l-IO inclusive.CHJ-(CHtn (CH,),-CH OH n has a statistical average value betweenlinclusive p is an integer between O-lO inclusive and the prod- 25 uct n(p+2) is 2-4. wherem y 2. An oil-in-water emulsion comprising 30 to 6571R is selected from the group consisting of methyl water. 30 to 60% oiland as an emulsifier to of xa i d f h I f a compound having the formula:'iiig rom t 6 group conbbtmg 0 Ro-Lcnnom') -lm.+C H;,0(X)+,, H wherein Ris a lipophilic hydrocarbon residue of a member selected from the groupconsisting of hydroge- CHzOH nated lanolin. CH2o- -c2Hao(cH,oH+| ,CH

cinoH and CH O-[-C H;,O(CH,OH-)l CH CHOHCH- (CHQ -CH OH m has astatistical average value between l-lO inclu- (CH).,C =i sive 40 n has astatistical average value between l-5 inclusive, p is an integer between0-10 inclusive and the prodwherein x y 10 and uct n (p+2) lies between2-12 inclusive.

4. The skin treating cream composition of claim 3 wherein said compoundis present in an amount of 5 to 25 percent by weight of saidcomposition.

5. A skin treating cream composition comprising at (Ha-(CHM cH cH 0Hleast one oil retention ingredient selected from the group consistingoflanolin alcohol and microcrystalline wax, and an emulsifying amount ofa compound having the formula wherein X +y l I wherein R is a lipophilichydrocarbon residue of a R Selected from the group conslstmg of methylmember selected from the group consisting of hydrogeand nated lanolin,

X is selected from the group consisting of -CH2OH.

(CH2),CH20H CH-,OH S CH O[C H O(cH OH-k-hckcihokl (CHMFCHA and +iCH CHOHCH CH 0 CH-OH 5629 3 z 2 wherein x y 10 and m has a statistical averagevalue between l-lO inclusive. n has a statistical average value between1-5 inclusive,

:i"( 2) (CH- L-CPQOH,

p is an integer between 1-10 inclusive and the product n (p+2) isgreater than about 4 and up to 12.

9 10 wherein x +y 12, v

R'is selected from the group consisting of methyl and ethyl, (CH l,,CH:,X is selected from the group consisting of CH OH.

wherein x and 0H. wherein x y 12. m has a statistical average valuebetween ll0 mclu- R i l t d from the group consisting of methyl slve,and ethyl. n has a statistical average value between 15 mclul5 X isSelected f the group consisting f SW8, CH2OH. p is an integer between0-10 inclusive and the product n (p+2) lies between 2l2 inclusive. 6.The skin treating cream composition of claim 5 wherein said compound ispresent in an amount of 5 to 30 percent by weight of said composition.

7. A cosmetic composition comprising a powdered and pigment selectedfrom the group consisting of iron ox- 2 H f mamum oxlde and f' Sulfateand a 25 m has a statistical average value between l-l0 inclulng agent acompound having the formula sive n has a statistical average valuebetween l5 inclusive, R0 HO R CH;O(X) H J p is an integer between 0-10inclusive and the product n (p+2) lies between 2l2 inclusive, said com-Whereifl R is a liPophilic hydrocaworl residue of a pound being presentin an amount sufficient to member selected from the group consisting ofhydrogepeptize Said pigment in said Composition. nated lanolin,

1. A water-in-oil emulsion comprising 20 to 70% water, 25 to 70% oil andas an emulsifier, 5 to 25% of a compound having the formula:RO-C2H3O(R'') )m ( C2H3O(X))n H wherein R is a lipophilic hydrocarbonresidue of a member selected from the group consisting of hydrogenatedlanolin,
 2. An oil-in-water emulsion comprising 30 to 65% water, 30 to60% oil and as an emulsifier 10 to 25% of a compound having the formula:RO-C2H3O(R'') )m ( C2H3O(X))n H wherein R is a lipophilic hydrocarbonresidue of a member selected from the group consisting of hydrogenatedlanolin,
 3. A skin treating cream composition comprising a water-in-oilor oil-in-water medium and an emulsifying amount of a compound havingthe formula RO-C2H3O(R'') )m ( C2H3O(X))n H wherein R is a lipophilichydrocarbon residue of a member selected from the group consisting ofhydrogenated lanolin,
 4. The skin treating cream composition of claim 3wherein said compound is present in an amount of 5 to 25 percent byweight of said composition.
 5. A skin treating cream compositioncomprising at least one oil retention ingredient selected from the groupconsisting of lanolin alcohol and microcrystalline wax, and anemulsifying amount of a compound having the formula RO-C2H3O(R'') )m (C2H3O(X))n -H wherein R is a lipophilic hydrocarbon residue of a memberselected from the group consisting of hydrogenated lanolin,
 6. The skintreating cream composition of claim 5 wherein said compound is presentin an amount of 5 to 25 percent by weight of said composition.
 7. ACOSMETIC COMPOSITION COMPRISING A POWDERED PIGMENT SELECTED FROM THEGROUP CONSISTING OF IRON OXIDE, TITANIUM OXIDE AND BARIUM SULFATE AND ASA PEPTIZING AGENT A COMPOUND HAVING THE FORMULA